US4880859A - Light-stabilized star polymer microparticles - Google Patents

Light-stabilized star polymer microparticles Download PDF

Info

Publication number
US4880859A
US4880859A US07/202,741 US20274188A US4880859A US 4880859 A US4880859 A US 4880859A US 20274188 A US20274188 A US 20274188A US 4880859 A US4880859 A US 4880859A
Authority
US
United States
Prior art keywords
polymer
microparticles
monomers
polymerization
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07/202,741
Other languages
English (en)
Inventor
Mario Slongo
Jean Rody
Franciszek Sitek
Andreas Valet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
Ciba Geigy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy Corp filed Critical Ciba Geigy Corp
Assigned to CIBA-GEIGY CORPORATION reassignment CIBA-GEIGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: CIBA-GEIGY AG, A SWISS CO.
Application granted granted Critical
Publication of US4880859A publication Critical patent/US4880859A/en
Assigned to CIBA SPECIALTY CHEMICAL CORPORATION reassignment CIBA SPECIALTY CHEMICAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CIBA-GEIGY CORPORATION
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers

Definitions

  • the present invention relates to light-stabilized star polymer microparticles, to processes for the preparation thereof, to their use in coating compositions and to coating compositions which contain such microparticles, and also to the "living" microparticles obtained in the preparation of the star polymer microparticles.
  • Coating compositions with a high proportion of film-forming material have been disclosed, for example, in EP-A 3,166 and EP-A 119,051 and in the literature cited in each of these; they have in general the structure of a liquid continuous phase and a disperse phase which, if appropriate, contains a high proportion of insoluble polymer microparticles.
  • the resulting films and coatings have a composite character, namely a polymer matrix or a continuous phase derived from polymer which was originally in solution, and a disperse phase derived from the polymer microparticles.
  • WO-A-86/00,626 and US-A 4,695,607 have disclosed star polymer microparticles, including "living" microparticles, which can also be used for the purposes described above.
  • Coating compositions containing such microparticles have only inadequate light stability, since hitherto only the coating mixture as such has been stabilized by physical admixture of a light stabilizer to the homogeneous liquid phase.
  • the present invention therefore relates, under a first aspect, to light-stabilized star polymer microparticles containing
  • microparticles having at least 5 up to 2,000,000 such arms, these arms consisting of one or more groups of different polymer types, and
  • polymer microparticles contain 0.1 to 30% by weight, relative to the monomers employed, of one or more light stabilizer(s).
  • these microparticles have a polydispersity of the arms of 1.3 to 1.6 and a polydispersity of the total microparticles of 1.3 to 1.6.
  • the microparticles described contain a single group or two groups of arms, especially 1 group of arms.
  • a further embodiment of the present invention relates to light-stabilized, soluble star polymer polymer microparticles containing
  • microparticles having at least 5 up to 2,000,000 arms, the ratio of the number of arms to the number of bifunctional recurring acrylic units in the core being ⁇ 1:1, and these polymer microparticles containing 0.1 to 30% by weight, relative to the monomers employed, of one or more light stabilizer(s).
  • microparticles are preferably obtained by means of a polymerization initiator in a molar initiator/bifunctional acrylic monomer ratio of ⁇ 1:1, whereby a crosslinked core is formed without the reaction mixture gelling.
  • “Soluble” is to be understood as meaning that nothing precipitates from a 1% solution in toluene, ethylene glycol dimethyl ether and/or tetrahydrofuran when the solution is centrifuged for 30 minutes at 17,000 r.p.m.
  • the arms solubilize the core.
  • the star polymer microparticles according to the invention are prepared with particular advantage by group transfer polymerization.
  • a particularly preferred embodiment of the present invention therefore relates to light-stabilized, "living" star polymer microparticles containing
  • At least part of the polymerization of the monomers is carried out in the presence of the light stabilizer(s).
  • Microparticles are here to be understood as meaning polymer particles of a size or size distribution within colloidal dimensions (for example about 0.01-20 ⁇ m), which particles are insoluble in the continuous liquid phase of coating compositions.
  • the expression polymer microparticle is well known in coating technology and hence in the relevant literature.
  • An essential feature of the microparticles, apart from their size, is that they contain or consist of a crosslinked core. In the ideal form, the microparticles have an approximately spherical shape.
  • the term “microgel” is also usual in the literature. Therefore, the microparticles according to the invention can also be described as light-stabilized polymer microgels. Both terms are used in the present application, and they are synonymous.
  • Examples of preferred monomers used for microparticles according to the invention and containing a C--C double bond, which is polymerizable by group transfer polymerization are: ##STR3## and mixtures thereof, in which A is CN, ##STR4## B is H, CH 3 , CN or --COOE, with the proviso that, in the case of ##STR5## B is H or CH 3 , A' is--OSi(E 1 ) 3 , --E, --OE or --NE'E", each E 1 independently of one another being C 1 -C 10 alkyl, C 6 -C 10 aryl or C 1 -C 6 alkyl-C 6 -C 10 aryl, E is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, dienyl, C 6 -C 20 cycloalkyl, C 6 -C 10 aryl, C 1 -C 6 alkyl-C 6 -C 10 aryl or phenyl-C 1
  • Preferred group transfer catalyst centres in "living" polymer microparticles are those of the formula (E 1 ) 3 M, in which E 1 is as defined above and M is Si, Sn or Ge.
  • star polymer microparticles according to the invention contain
  • Q is a group of the formula (E 1 ) 3 M as defined above.
  • microparticles according to the invention are prepared, as already mentioned, with particular advantage by means of group transfer polymerization, at least one polymerization step being carried out in the presence of the light stabilizer(s) (addition of the latter to the monomers before the polymerization, during the polymerization or towards the end of the polymerization).
  • Group transfer polymerization is known per se and can be carried out by the processes described in the literature.
  • the group transfer polymerization processes described in WO-A-86/00,626 or US-A 4,695,607 and the processes known from the literature references cited therein are used with particular advantage.
  • WO-A-86/00,626 and US-A 4,695,607 are to be understood as a part of the present description.
  • group transfer polymerization is here to be understood as a process in which the polymerization of monomers having C--C double bonds is initiated by various initiators of the formula Q--Z, in which Z is an activating substituent which is bound to one end of the growing polymer molecule, and Q is a group which continuously migrates to the other end of the growing polymer molecule, as more monomer is being added to the polymer molecule.
  • the polymerization of a monomer ##STR7## initiated by the initiator Q--Z proceeds as follows: ##STR8##
  • the group Q is thus an active centre and can initiate the addition of further monomers.
  • a polymer molecular having a group Q is termed a "living" polymer and the group Q itself is termed a "living" group transfer polymerization centre.
  • Group transfer polymerization methods are especially used for the preparation of the light-stabilized star polymer microparticles according to the invention which, in addition to WO-A-86/00,626, are partly also described in US-A 4,414,372, 4,417,034, 4,508,880 and 4,524,196, which are likewise to be regarded as part of the present description.
  • Group transfer polymerizations give a "living" polymer when, for example, an initiator of the formula (E 1 ) 3 MZ is used for initiating the polymerization of a monomer having a C--C double bond.
  • the group Z is an activating substituent (as described above) which is bound to one end of the "living" polymer molecule.
  • the group (E 1 ) 3 M adds to the other end, the "living" end, of the polymer molecule.
  • the resulting "living" polymer molecule can itself function as an initiator for the polymerization of the same or another monomer to form a new "living" polymer molecule, with Z at one end and (E 1 ) 3 M at the other ("living") end.
  • the "living" polymer can then be deactivated, if desired, for example by reaction with a proton source, for example an alcohol.
  • step (a) or/and (b) being carried out in the presence of 0.1 to 30% by weight, relative to the monomers, of one or more light stabilizer(s).
  • a "living" polymer (the arm) is prepared by reacting a monomer A containing a C--C double bond with a group transfer initiator (E 1 ) 3 MZ.
  • the resulting "living" polymer is reacted with a polyfunctional compound (monomer B) which contains at least 2 polymerizable C--C double bonds in the molecule.
  • This gives a star polymer microparticle with arms of polymerized monomer A, which are polymerized onto a crosslinked core of polymerized monomer B.
  • the active group transfer centres in the core can be deactivated by reaction with a proton source.
  • the light stabilizer(s) can be added in both polymerization steps or in only one of them. Accordingly, polymer microparticles are formed which are light-stabilized in the core, in the arms or in both of these parts.
  • step (b) reacting the resulting "living" core with one or more monomers having a C--C double bond and polymerizable by group transfer polymerization, step (a) or/and (b) being carried out in the presence of 0.1 to 30% by weight, relative to the monomers, of one or more light stabilizer(s).
  • a "living" core is prepared by reacting a group transfer initiator (E 1 ) 3 MZ with a polyfunctional compound (monomer B) containing at least 2 polymerizable C--C double bonds per molecule.
  • This "living" core is then reacted with a monomer A (as described above), whereby a star polymer microparticle having arms of polymerized monomer A, which are polymerized onto the crosslinked core of polymerized monomer B, is formed.
  • the active group transfer centres at the ends of the arms can be reacted with further monomers or can be deactivated by reaction with a proton donor.
  • the light stabilizer(s) can be added in both polymerization steps or in only one of them. Accordingly, polymer microparticles are formed which are light-stabilized in the core, in the arms or in both of these parts.
  • step (c) reacting the resulting "living" polymers with one or more monomers which contain a C--C double bond and which are polymerizable by group transfer polymerization, these monomers being identical to or different from those employed in step (a),
  • steps (a), (b) or/and (c) being carried out in the presence of 0.1 to 30% by weight, relative to the monomers, of one or more light stabilizer(s).
  • a "living" polymer (the first arms) are prepared by reacting a monomer A, which contains a polymerizable C--C double bond in the molecule, with a group transfer initiator (E 1 ) 3 MZ.
  • the resulting "living" polymer is then reacted with a polyfunctional compound (monomer B) which contains at least 2 polymerizable C--C double bonds in the molecule.
  • the resulting polymer has arms of polymerized monomer A, which are polymerized onto a crosslinked core of polymerized monomer B, the core still containing "living" group transfer centres.
  • This polymer is then reacted with a third monomer C containing a polymerizable C--C double bond, whereby further arms consisting of polymerized monomer C are polymerized onto the core.
  • the nature and quantity (mole number) of C can here be the same as those of A or different.
  • the two types of arms can have different molecular weights or/and be derived from different monomers. If 2 or more types of "living" group transfer centres are introduced into the core and functional groups of different reactivity are used in the arms, polymer microparticles with more than 2 different types of arms are obtained.
  • the light stabilizer(s) can be added in the 3 polymerization steps, in only one of them or in any two of them. Accordingly, polymer microparticles are formed which are light-stabilized in the core, in one type of arm, in all types of arms, in the core and one type of arm or in the core and all types of arms.
  • the polyfunctional compounds used can be any molecules containing at least 2 ethylenic C--C double bonds. Examples of these are: ethylene dimethacrylate, 1,3-butylene dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, di- and tri-ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1,6-hexylene dimethacrylate, 1,4-butylene dimethacrylate, ethylene diacrylate, 1,3-butylene diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, 1,6-hexylene diacrylate, 1,4-butylene diacrylate and allyl methacrylate.
  • Examples of monomers having one double bond polymerizable by group transfer polymerization are substituted or unsubstituted alkyl esters of methacrylic acid, such as methyl, ethyl, butyl, hexyl and 2-ethylhexyl methacrylate and 2-isocyanoethyl methacrylate. Methyl, ethyl and 2-ethylhexyl methacrylate are preferred.
  • starting monomers which can be used according to the invention, of catalysts, solvents, initiators, reaction schemes and calculation methods can be taken from pages 17 to 24 of WO-A-86/00,626 or column 11, line 40 to column 16, line 46 of US-A 4,695,607, and are to be understood as disclosed in the present description.
  • initiators 1-trimethylsiloxy-1-isobutoxy-2-methylpropene and 1-(2-trimethylsiloxyethoxy)-1-trimethylsiloxy-2-methylpropene.
  • catalysts are tris-(dimethylamino)-sulphonium bifluoride (TASHF 2 ), tetrabutylammonium bifluoride (TBAHF 2 ), tetrabutylammonium fluoride (TBAF) and tetrabutylammonium chlorobenzoate (TBACF).
  • TASHF 2 tris-(dimethylamino)-sulphonium bifluoride
  • TAAHF 2 tetrabutylammonium bifluoride
  • TBAF tetrabutylammonium fluoride
  • TBACF tetrabutylammonium chlorobenzoate
  • solvents which can be used are 1,2-dimethoxyethane, acetonitrile, xylene and tetrahydrofuran.
  • the light stabilizers which are contained in the star polymer microparticles according to the invention and which, as described above, are present during the polymerization in at least one polymerization step during the preparation of the microparticles, can be chemically anchored in the polymer (the light stabilizer participates in the polymerization) or only be physically occluded. Both cases give the desired light stabilization, but chemical incorporation is preferred.
  • Representatives of virtually all known classes of light stabilizers for example sterically hindered amines, 2-(2-hydroxyphenyl)-benzotriazoles, oxalic acid anilides, 2-hydroxybenzophenones, hydroxyphenyltriazines or cinnamic acid derivatives, can be used for the light stabilization of the microparticles.
  • the preferred light stabilizers here are 2-(2-hydroxyphenyl)-benzotriazoles and especially sterically hindered amines.
  • the light stabilizer belongs to the class of sterically hindered amines
  • these are preferably cyclic amines, in particular derivatives of 5-membered, 6-membered or 7-membered heterocyclic ring systems with 1 or 2 N atoms, which have tertiary C atoms in both the ortho-positions to the N atom, thus effecting steric hindrance of the N atom.
  • ring systems examples include 2,2,5,5-tetrasubstituted pyrrolidines, imidazolidones or oxazolines of the formulae ##STR12## or 2,2,6,6-tetrasubstituted piperazinones and piperazinediones of the formulae ##STR13## or diazacycloheptanones of the formula ##STR14## in which R 1 , R 2 , R 3 and R 4 are aliphatic hydrocarbon radicals which may be combined to form spiro rings, R 5 and R 7 are hydrogen or alkyl and X is hydrogen, oxyl oxygen or a monovalent organic radical and Y is hydrogen or a monovalent or divalent organic radical, for example a compound of the formula ##STR15## Decahydroquinolines disubstituted in the 2-position are also representatives of sterically hindered amines.
  • 2,2,6,6-tetraalkylpiperidine derivatives are of particular importance. These are compounds which contain in their molecule at least one group of the formula I ##STR16## in which R is hydrogen or methyl.
  • the light stabilizer can contain one or more such groups of the formula I, for example it can be a mono-, bis-, tris-, tetra- or oligo-piperidine compound.
  • Those piperidine derivatives are preferred which contain one or more groups of the formula I, in which R is hydrogen, and those in which the ring nitrogen does not carry a hydrogen atom.
  • n is a number from 1 to 4, preferably 1 or 2
  • R is hydrogen or methyl
  • R 1 is hydrogen, oxyl, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 18 alkenyloxy, C 7 -C 12 aralkyl, C 2 -C 8 alkanoyl, C 3 -C 5 alkenoyl, C 2 -C 8 alkanoyloxy-C 1 -C 4 alkyl, C 3 -C 8 alkenoyloxy-C 1 -C 4 alkyl or glycidyl, R 1 preferably being C 1 -C 12 alkyl, allyl, benzyl, acetyl, (meth)acryloyl or (meth)acryloyloxyeth
  • Any C 1 -C 12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • C 1- C 18 Alkyl radicals R 1 or R 2 can be, for example, the groups listed above and in addition also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • Examples of C 1 -C 18 alkoxy are the alkoxy groups derived from the above alkyl groups.
  • a C 3 -C 8 -alkenoyloxy-C 1 -C 4 alkyl radical R 1 is, for example, C 3 -C 5 alkenoyl-oxy-C 1 -C 2 alkyl, especially (meth)acryloyloxyethyl.
  • a C 3 -C 8 alkenyl radical R 1 can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.
  • a C 3 -C 8 alkynyl radical R 1 is preferably propargyl.
  • Cycloalkyl(oxy) is preferably C 5 -C 7 cycloalkyl(oxy), especially cyclohexyl(oxy).
  • a C 7 -C 12 aralkyl radical R 1 is in particular phenethyl or especially benzyl.
  • a C 1 -C 8 alkanoyl radical R 1 is, for example, formyl, propionyl, butyryl, octanoyl or preferably acetyl, and C 3 -C 5 alkenoyl is especially acryloyl.
  • a monobasic radical R 2 of a carboxylic acid is, for example, an acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid or benzoic acid radical.
  • a dibasic radical R 2 of a dicarboxylic acid is, for example, a malonic acid, adipic acid, suberic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, or bicycloheptenedicarboxylic acid radical.
  • a tribasic radical R 2 of a tricarboxylic acid is, for example, a trimellitic acid or nitrilotriacetic acid radical.
  • a tetrabasic radical R 2 of a tetracarboxylic acid is, for example, the tetrabasic radical of butane-1,2,3,4-tetracarboxylic acid or pyromellitic acid.
  • a dibasic radical R 2 of a dicarbamic acid is, for example, a hexamethylenedicarbamic acid or 2,4-toluylene-dicarbamic acid radical.
  • n 1 or 2
  • R is hydrogen
  • tetraalkylpiperidine compounds of the formula II are the following:
  • Any C 5 -C 7 cycloalkyl substituents are especially cyclohexyl.
  • a C 7 -C 8 aralkyl radical R 3 is in particular phenylethyl or especially benzyl.
  • a C 2 -C 18 alkanoyl radical R 3 is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, and preferably acetyl, and C 3 -C 5 alkenoyl is especially acryloyl.
  • a C 2 -C 8 alkenyl radical R 4 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
  • a C 1 -C 4 alkyl radical R 4 which is substituted by a cyano, alkoxycarbonyl or carbamide group can be, for example, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl or 2-(dimethylaminocarbonyl)-ethyl.
  • Any C 2 -C 12 alkylene substituents are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • Any C 6 -C 15 arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene, 4,4'-diphenylene or ##STR19## in which D 1 and D 2 independently of one another are hydrogen or methyl.
  • a C 6 -C 12 cycloalkylene radical D is especially cyclohexylene.
  • R and R 1 are as defined and preferred under (a)
  • tetraalkylpiperidine compounds of the formula III are the following: (27) N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-hexamethylene-1,6-diamine, (28) N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-hexamethylene-1,6-diacetamide, (29) 1-acetyl-4-(N-cyclohexylacetamido)-2,2,6,6-tetramethylpiperidine, (30) 4-benzoylamino-2,2,6,6-tetramethyl piperidine, (31) N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-N,N'-dibutyladipamide, (32) 1,2,2,6,6-pentamethyl-4-maleimido-piperidine, (32a) 1-acetyl-2,2,6,6-tetramethyl-4-maleimido-piperidine, (3
  • a C 2 -C 8 alkylene radical R 5 is, for example, ethylene, 1-methylethylene, propylene or 2-ethylpropylene.
  • a C 4 -C 22 acyloxyalkylene radical R 5 is, for example, 2-ethyl-2-acetoxymethylpropylene.
  • tetraalkylpiperidine compounds from this class are the following compounds: (38) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane, (39) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane, (40) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane, (41) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane and (42) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-s
  • Any C 1 -C 12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • Any C 1 -C 18 alkyl substituents can, for example, be the groups listed above and additionally also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • Any C 2 -C 6 alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
  • a C 3 -C 5 alkenyl radical R 7 is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
  • C 7 -C 9 Aralkyl radicals R 7 , T 1 and T 2 are in particular phenethyl or especially benzyl.
  • T 1 and T 2 forming a cycloalkane ring together with the C atom can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
  • C 6 -C 10 Aryl radicals R 7 , T 1 and T 2 are in particular phenyl, ⁇ - or ⁇ -naphthyl which are unsubstituted or substituted by halogen or C 1 -C 4 alkyl.
  • a C 2 -C 12 alkylene radical R 7 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • a C 4 -C 12 alkenylene radical R 7 is in particular 2-butenylene, 2-pentenylene or 3-hexenylene.
  • a C 6 -C 12 arylene radical R 7 is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
  • a C 2 -C 12 alkanoyl or C 3 -C 8 alkenoyl radical Z' is, for example, propionyl, butyryl, octanoyl or dodecanoyl, and preferably acetyl, acryloyl or methacryloyl.
  • those of the compounds of the formulae VA, VB and VC are preferably used in which at least one of the substituents contains an ethylenic double bond. See also the preferred definitions of R 1 in the formula II.
  • tetraalkylpiperidine compounds from this class are the following compounds: (43) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione, (44) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione, (45) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione, (46) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione, (47) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane, (48) 2,2-dibutyl
  • a C 2 -C 6 alkylene radical A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
  • R 11 and R 12 together are C 4 -C 5 alkylene or oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
  • tetraalkylpiperidine compounds from this class are the compounds of the following formulae: ##STR29## and compounds 56-63 which, in place of the methyl group on the piperidine nitrogen, carry an ethylenically unsaturated substituent as specifically defined for R' under the formula II.
  • Oligomeric or polymeric compounds the recurrent structural unit of which contains a 2,2,6,6-tetraalkylpiperidine radical of the formula (I), in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof, which contain such radicals.
  • a 2,2,6,6-tetraalkylpiperidine radical of the formula (I) in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof, which contain such radicals.
  • 2,2,6,6-tetraalkylpiperidine light stabilizers from this class are the compounds of the following formulae, m being a number from 2 to 200.
  • m being a number from 2 to 200.
  • those sterically hindered amines are preferred which contain ethylenically unsaturated groups, for example allyl, vinyl or maleate groups, and in particular acrylic or methacrylic groups, which copolymerize with the monomers. Therefore, those compounds of the formulae defined in the above sections (a) to (f) can be used preferably according to the invention which contain an ethylenic double bond in at least one of the substituents.
  • the light stabilizers from the class of sterically hindered amines are known, for example, from EP-A 114,784 and can be prepared by known processes.
  • UV absorbers Another group of light stabilizers, which is also important besides the hindered amine type, are the UV absorbers which belong to various classes of compounds. UV absorbers are also suitable for stabilizing polymer microparticles, according to the invention.
  • the first class of such UV absorbers is represented by the 2-(2-hydroxyphenyl)-benzotriazoles, of which the following structural types are particularly suitable for the polymer microparticles according to the invention:
  • R 16 is C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl, straight-chain or branched C 2 -C 18 alkenyl, C 6 -C 14 aryl, C 7 -C 15 alkaryl, C 7 -C 15 aralkyl or ##STR35##
  • R 17 and R 18 independently of one another are H, straight-chain or branched C 1 -C 18 alkyl, straight-chain or branched C 3 -C 18 alkyl which is interrupted once or several times by --O-- or --NR 19 --, C 5 -C 12 cycloalkyl, C 6 -C 14 aryl, C 7 -C 15 alkaryl, C 7 -C 15 aralkyl or straight-chain or branched C 3 -C 8 alkenyl, or R 17 and R 18 together with the N atom, to which they are linked, form a pyrrolidine, piperidine, piperazine or morpholine ring, R 19 is H or straight-chain or branched C 1 -C 18 alkyl, R 22 is straight-chain or branched C 1 -C 18 alkyl or C 3 -C 18 alkenyl, C 5 -C 12 cycloalkyl, C 6 -C 14 aryl, C 7 -C 15 aralky
  • An alkyl radical R 14 can be, for example, methyl, ethyl, propyl, isopropyl, butyl and tert-butyl, and an alkoxy radical R 14 can be, for example, methoxy, ethoxy, propoxy and butoxy.
  • R 16 , R 17 , R 18 , R 19 , R 21 and R 22 can, for example, be the following alkyl radicals: methyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, 2-ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-dodecyl, 1,1,7,7,-tetramethyloctyl and n-octadecyl.
  • R 17 and R 18 can, for example, be the following C 3 -C 18 alkyl radicals which are interrupted by --S--, --O-- or --NR 19 --: methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl, CH 3 OCH 2 CH 2 OCH 2 CH 2 --, CH 3 CH 2 OCH 2 CH 2 OCH 2 CH 2 --, C 4 H 9 OCH 2 CH 2 OCH 2 CH 2 --, dodecyloxypropyl, --CH 2 CH 2 --NH--C 4 H 9 , --CH 2 CH 2 CH 2 NH--C 8 H 17 and ##STR37##
  • R 16 , R 17 , R 18 and R 22 can, for example, be the following C 5 -C 12 -cycloalkyl radicals: cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl.
  • R 17 and R 18 can, for example, be the following alkenyl radicals: allyl, methallyl, 2-n-hexenyl and 4-n-octenyl.
  • alkenyl radical R 16 can be as defined for alkenyl radicals R 17 and R 18 or it can, for example, be --CH ⁇ CH 2 , 10-n-undecenyl or 9-n-octadecenyl.
  • R 16 , R 17 , R 18 , R 21 and R 22 independently of one another can, for example, be the following C 7 -C 15 aralkyl radicals: benzyl, ⁇ -phenylethyl, ⁇ -phenylethyl and 4-tert-butylbenzyl.
  • R 16 , R 17 , R 18 and R 22 independently of one another can, for example, be the following C 6 -C 14 aryl radicals: phenyl, ⁇ -naphthyl and ⁇ -naphthyl.
  • Alkaryl radicals R 16 , R 17 , R 18 , R 21 or R 22 can be a tolyl, xylyl, ethylphenyl, isopropylphenyl, n-butylphenyl, tert-butylphenyl, octylphenyl, di-tert-butylphenyl or nonylphenyl radical.
  • Alkyl in an --SO 2 --C 1 -C 4 alkyl radical R 21 can be a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl radical.
  • Aryl in an --SO 2 --C 6 -C 14 aryl radical R 21 is, for example, phenyl, ⁇ -naphthyl or ⁇ -naphthyl.
  • Alkaryl in an --SO 2 --C 7 -C 18 alkaryl radical R 21 independently is as defined for R 16 .
  • C 2 -C 8 Alkylene radicals R 23 and R 25 can, for example, be the following radicals: ethylene, propylene, butylene, hexylene and octylene.
  • An alkylene radical R 24 can independently be as defined for R 23 or, in addition, can also be a higher-molecular group such as decylene or dodecylene.
  • a C 4 -C 8 alkenylene radical R 23 can, for example, be the following group: butenylene.
  • Straight-chain or branched C 4 -C 10 alkylene groups interrupted by --O-- in the case of R 23 and R 25 can, for example, be the following groups:
  • Typical representatives of compounds of the formula VII in which m is the number 1 are the following: 2-[2-hydroxy-3-R o -5-(2-carbomethoxyethyl)phenyl]-benzotriazole, 2-[2-hydroxy-3-R o -5-(2-carbomethoxyethyl)-phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-3-R o -5-(2-carbocyclohexyloxyethyl)phenyl]-benzotriazole, 2-[2-hydroxy-3-R.sub.o -5-(2-carbooctyloxyethyl)phenyl]-benzotriazole, 2-2-hydroxy-3-R o -5-[2-carbo-(2-ethylhexyloxy)ethyl]-phenyl-benzotriazole, 2-[2-hydroxy-3-R oisodecyloxyethyl)-phenyl]-phenyl]-
  • Typical representatives of compounds of the formula VII in which m 1 is the number 2 are the following: ##STR39## Further preferred compounds of the formula VII are: 2-[2-hydroxy-3-R o -5-(2-carbo-n-octyloxyethyl)-phenyl]-benzotriazole, 2- 2-hydroxy-3-R o -5-[2-carbo-(2-ethylhexyl)-oxyethyl]-phenyl -benzotriazole, 2-[2-hydroxy-3-R o -5-(2-carbo-n-octyloxyethyl)-phenyl]-5-chlorobenzotriazole and 2- 2-hydroxy-3-R o -5-[2-carbo-(2-ethylhexyl)-oxyethyl]-phenyl -5-chlorobenzotriazole, and the compound of the formula ##STR40## In all the above compound names and formulae, R o is H, CH 3 or
  • Substituted or unsubstituted C 1 -C 18 alkyl radicals R 27 and R 28 can here independently of one another be as defined above for R 16 .
  • Aralkyl radicals R 27 and R 28 can independently of one another be, for example, benzyl, ⁇ -phenylethyl, ⁇ -phenylethyl, ⁇ , ⁇ -dimethylbenzyl or 4-tert-butylbenzyl.
  • a substituted C 1 -C 18 alkyl radical R 29 is here preferably substituted by epoxy groups and particularly preferably by one epoxy group.
  • a C 1 -C 18 alkyl radical R 32 can here be as defined above for R 16 and preferebly is unsubstituted C 1 -C 12 alkyl.
  • Examples of 2-(2-hydroxyphenyl)-benzotriazoles of this structural type are: ##STR49## and the compounds of the above formulae in which H or CH 3 takes the place of the t-alkyl radicals in the p-position to the hydroxyl group.
  • R 46 is hydrogen or Cl
  • X is O or NH, especially O
  • m is 2
  • n is 1
  • Z is C 2 -C 6 alkylene, cyclohexylene or phenylene
  • Y is O or NH, especially O
  • benzotriazoles of the formula XI are: (2-(meth)acrylyloxy)cyclohexyl 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-R o -benzenepropanote, (2-(meth)acrylyloxy)-cyclohexyl 3(5-chloro-2H-benzotriazol-2-yl)-4-hydroxy-5-R o -benzenepropanoate, N-(2-(meth)acrylyloxyethyl)-3-(2H-benzotriazol-2-yl)-4-hydroxy-5-R o -benzenepropanamide, N-(2-(meth)acrylyloxyethyl)-3-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxy-5-R o -benzenepropanamide, N-(3-(meth)acrylyloxypropyl)-3-(2H-benzotriazol-2-y
  • R o is H, CH 3 or t-butyl, H and CH 3 being preferred.
  • a substituted or unsubstituted alkyl radical R 48 can here be, for example, as defined above for R 16 .
  • the 2-(2-hydroxyphenyl)-benzotriazoles which can be used as light stabilizers for the microparticles are known or can be prepared by methods known per se, for example according to EP-A 57,160, EP-A 133,165 and other documents, known to those skilled in the art, relating to 2-(2-hydroxyphenyl)-benzotriazoles.
  • Most of the light stabilizers (piperidine light stabilizers and UV absorbers) described in this application are also described in EP-A 226,538.
  • a further type of suitable light stabilizers from the UV absorber group is represented by 2-hydroxybenzophenones which have, for example, a structure according to the formula XIII ##STR54## in which R 33 is straight-chain or branched C 1 -C 18 alkyl which may be interrupted once or several times by --O-- and is unsubstituted or substituted by epoxy groups, or is ##STR55##
  • 2-hydroxybenzophenones examples include the 4-methoxy, 4-octyloxy, 4-decyloxy or 4-dodecyloxy derivatives, and these may be substituted by epoxy groups.
  • UV absorbers comprise 2,4-bis-(2'-hydroxyphenyl)-6-alkyl-s-triazines, for example the 6-ethyl, 6-heptadecyl or 6-undecyl derivatives, and oxalic acid diamides, in particular oxalic acid dia-nilides, for example 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxanilide and its mixture with 2-ethoxy-2'-
  • R 34 is straight-chain or branched C 1 -C 18 alkyl which may be interrupted by --O--
  • R 35 is hydrogen, C 1 -C 4 alkyl, methoxy or phenyl
  • R 36 and R 37 independently of one another are cyano or --C(O)OR 38 groups and R 38 is straight-chain or branched C 1 -C 18 alkyl which may be interrupted by --O--.
  • cinnamic acid derivatives examples include ethyl and isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl ⁇ -carbomethoxy-cinnamate and methyl ⁇ -cyano- ⁇ -methoxycinnamate.
  • those light stabilizers are preferred which can be chemically anchored in, that is to say copolymerized into, the polymer microparticles according to the invention.
  • light stabilizers in particular those from the classes defined above, which contain at least one reactive substituent with at least one ethylenic double bond.
  • 2,2,6,6-tetraalkylpiperidine derivatives in particular those listed in the above section (a) to (f)
  • 2-(2-hydroxyphenyl)-benzotriazoles as well as mixtures of these two types of light stabilizers (in particular those listed in the above sections (A) to (F))
  • the compounds of the formulae II, III, IV, VA-VC and VI especially those of the formulae II, III, VA and VI
  • those of the formulae VII, IX, X, XI and XIa are here to be mentioned in particular.
  • compunds of the type of the formulae II, III and XI are employed.
  • those light stabilizers are advantageously used for microparticles according to the invention, which can be prepared by group transfer polymerization, which do not contain any such groups, for example --OH, COOH-- or other acid groups. However, it depends on the position of such groups in the molecule whether they have the said effect.
  • the OH group in the phenyl radical of the 2-(2-hydroxyphenyl)benzotriazole UV absorbers hardly interferes, if at all, with the polymerization, depending on the further substitution, and especially does not interfere if there are no tertiary substituents in the ortho-position to the OH group.
  • compounds having the last-mentioned substituents can be used for stabilizing the microparticles according to the invention, in particular for stabilizing the "arms" into which they are incorporated, for example terminally.
  • those hindered amines are also preferred according to the invention which carry a substituent other than H on the hindered N atom (i.e., for example, on the piperidine N atom).
  • the microparticles according to the invention can also be formed with hindered amines which are unsubstituted on the N atom.
  • the hindered amines should preferably not contain any OH and COOH groups.
  • the light stabilizer(s) is or are added in a quantity from 0.1 to 30% by weight and preferably 0.5 to 10.0% by weight, each relative to the monomers in the particular polymerization step.
  • the addition can be made at the start, together with the monomers, continuously during or towards the end of the polymerization process. In this way, uniform distribution of the light stabilizer(s) in the microparticles or enrichment in the outer layers is achieved. This ensures that the light stabilizer(s) is or are physically or chemically anchored in the resulting polymer microparticles depending on its (their) nature.
  • the light stabilizer carries reactive groups, for example ester, epoxy, isocyanate, amino or amide groups or especially ethylenic double bonds, for example in (meth)acrylate or vinyl groups, by means of which it can be chemically bonded to the polymer and, if appropriate, can participate directly in the polymerizartion as already explained above.
  • reactive groups for example ester, epoxy, isocyanate, amino or amide groups or especially ethylenic double bonds, for example in (meth)acrylate or vinyl groups, by means of which it can be chemically bonded to the polymer and, if appropriate, can participate directly in the polymerizartion as already explained above.
  • the invention also relates to dispersions which contain the polymer microparticles according to the invention.
  • the microparticles are not isolated as such but processed further as a dispersion in the solvent, in which the polymerization or the deactivation of the "living" groups took place, or in another dispersing medium.
  • the dispersants used can, in particular, be aromatic, aliphatic and cycloaliphatic hydrocarbons, but others, for example water, are also possible. Examples of hydrocarbons are benzene, toluene and especially higher-boiling aliphatic hydrocarbon fractions, for example those having a boiling range of 100°-200° C.
  • the dispersions according to the invention contain the microparticles, for example, in a quantity from 10 to 90%, in particular 20 to 80%, for example 40 to 80%, relative to the dispersion.
  • the invention also relates to coating compositions wherein the film-forming material comprises
  • phase (b) 99 to 5% by volume of a liquid continuous phase which has a viscosity of 0.1 to 30 poise at room temperature and is capable of curing to give a film-forming polymer, the total volume of (a) and (b) being 100% and the disperse phase preferably participating in curing the coating.
  • Phase (b) can here also contain one or more light stabilizers.
  • the disperse phase contains preferably at least 50% by volume of microparticles.
  • the film-forming material comprises 5 to 85, for example 15 to 85, % by volume of the disperse phase containing at least 50% by volume of microparticles according to the invention, and 95-15, for example 85-15%, by volume of the liquid continuous phase having a viscosity of 0.1 to 20 poise at room temperature.
  • the microparticles can here be added like an additive to a finished coating composition, or they can be employed in place of a corresponding porportion of the coating components, for example the acrylate or polyester component of a coating composition. In the latter case, the microparticles can participate (as a reactive component) in the curing of the coating.
  • the disperse phase can consist exclusively of polymer microparticles; however, in addition to the microparticles and, if appropriate, solvent, the disperse phase preferably also contains particles of pigment, filler and/or extender, such as are conventionally used in coating compositions. With advantage, these particles have a size of, for example, 0.1 to 5 ⁇ m, as is conventional in coating technology.
  • the polymer microparticles and the pigment, filler and/or extender particles are advantageously in a stable dispersion in a deflocculated state in the liquid continuous phase; this can be accomplished, for example, by means of known pigment dispersants.
  • the liquid film-forming material in the continuous phase or a chemical variant thereof can itself be an effective dispersant.
  • the dispersing of the pigment can be carried out in the manner customary in coating technology, for example with the use of ball mills, bead mills, attrition mills or colloid mills.
  • the disperse phase is capable of participating in the curing of the coating, presupposing that either the microparticle core or the dispersant part or both contain chemically reactive groups, by means of which they can participate in a curing reaction.
  • the capacity for participating in the curing reaction resides in the dispersant, the latter contains appropriate reactive groups, for example hydroxyl or carboxyl groups, which can be located in the solvated polymer part or in that part of the molecule which serves as an anchoring component for the microparticles.
  • the disperse phase/continuous phase system can also itself form a two-component system, i.e. the film formation is accomplished by a reaction of the two phases with one another.
  • polmer microparticles according to the invention that, as a constituent of coating compositions, then can, if appropriate, participate in the curing thereof by means of reactive groups capable of condensation polymerization.
  • reactive groups capable of condensation polymerization This can be accomplished, for example, by using ethylenically unsaturated monomers which contain, for example, hydroxyl or carboxyl groups.
  • ethylenically unsaturated monomers which contain, for example, hydroxyl or carboxyl groups.
  • hydroxyalkyl acrylates or methacrylates such as hydroxyethylacrylate or hydroxyisopropyl methacrylate
  • unsaturated carboxylic acids such as acrylic acid or methacrylic acid.
  • the other component of the coating compositions according to the invention is the liquid continuous phase which is capable of giving a polymer film when cured by means of addition or condensation polymerization.
  • Condensation polymerization is here to be understood as meaning in particular the polymerization by means of a reaction of pairs of functional groups with the formation of functional units which are not present in the monomers, in which case the reaction can, if appropriate, involve the evolution of low-molecular by-products.
  • Suitable constituents of the continuous phase are in particular curable or thermosetting resins which can be converted into a film-forming polymer by means of heating and/or addition of a catalyst.
  • curable or thermosetting resins which can be converted into a film-forming polymer by means of heating and/or addition of a catalyst.
  • examples of such resins are:
  • Phenol/formaldehyde resins i.e. the product of the reaction of phenols with formaldehyde.
  • Amino/formaldehyde resins for example urea/formaldehyde or melamine/formaldehyde resins, obtainable by reacting urea, melamine or other nitrogen-containing compounds with formaldehyde.
  • Crosslinkable acrylic resins which are derived from substituted acrylates, for example epoxy-acrylates, urethane-acrylates or polysteracrylates, and also acrylic resins which do not contain any olefinic double bond and he OH or/and COOH groups of which can participate in the condensation reaction.
  • Polyurethane resins based on the reaction of diisocyanates or polyisocyanates with polyhydroxy compounds.
  • Epoxide resins for example those obtained by reacting epichlorohydrin with bisphenol A.
  • the continuous phase can, in principle, consist of a single liquid substance or of a homogeneous liquid mixture of two or more substances.
  • a mixture of two or more substances is preferred, and this can be in the form of a one-component or two-component system.
  • the continuous liquid phase is a one-component system
  • this contains the film-forming constituents in a storage-stable form, and curing can take place, for example, by mere heating, or a curing agent is added.
  • Suitable one-component systems are built up, for example, from one of the said thermosetting resins and, if appropriate, a further liquid substance, the so-called reactive diluent, which contains reactive groups, by means of which it can participate in the curing of the film-forming material, and which especailly contributes to improved flexibility of the coat film.
  • the reactive diluent is, for example, a bifunctional monomer or oligomer having molecular weights up to about 1,000 and containing, in particular, OH groups, for example 2-6 OH groups.
  • Examples of these are simple glycols or polyols such as butane-1,4-diol, and especially hydroxy-terminated oligomeric esters of polyalcohols with polycarboxylic acids and/or monocarboxylic acids.
  • Examples of suitable reactive diluents are given in EP-A 3,166.
  • the continuous liquid phase is a two-component system, this is prepared only just before application of the finished coating composition, by combining two liquid components which are mutually reactive and, in addition, are capable of forming a film.
  • the second component can co-react with the first component and thus form a cured film, as is the case, for example, with two-component polyurethane coatings.
  • the second component can also be a catalyst for the curing reaction of the first component, the acid-catalyzed curing of amino resins being an example.
  • compositions are preferred according to the invention which are based on a crosslinkable acrylate, polyester/alkyd or polyurethane resin which, if appropriate, has been crosslinked with aminoplasts, polyisocyanate or polyepoxides.
  • the coating compositions according to the invention can, in the continuous phase, contain a catalyst for curing the coating, which catalyst is added, depending on the nature of the film-forming material used, preferably in a quantity from 0.1 to 15% by weight, relative to the total continuous phase including any reactive diluent present.
  • the catalyst is preferably an acidic catalyst or a catalyst which releases acid on heating, for example methanesulfonic acid, toluenesulfonic acid, phosphoric acid, half-esters of maleic acid, cyclohexylphosphonous acid, trichloroacetic acid, trifluoroacetic acid or a tetrahalogenophthalic acid and half-esters thereof.
  • an acidic catalyst or a catalyst which releases acid on heating for example methanesulfonic acid, toluenesulfonic acid, phosphoric acid, half-esters of maleic acid, cyclohexylphosphonous acid, trichloroacetic acid, trifluoroacetic acid or a tetrahalogenophthalic acid and half-esters thereof.
  • the coating compositions according to the invention can contain an inert liquid diluent, for example up to 50 and in particular 30% by volume, which volatilizes under the conditions of the application of the coating composition to a substrate.
  • suitable inert solvents are aromatic and aliphatic hydrocarbons, halogenated hydrocarbons, lower alcohols or water.
  • the film-forming material in the coating compositions according to the invention consists of 10 to 80, for example 20 to 80, % by volume of liquid continuous phase.
  • the coating compositions according to the invention can be applied to a substrate by means of any conventional method known to those skilled in the art, for example by brushing, spraying, dipping or electrophoretic appication.
  • the coatings and finishes based on the compositions according to the invention are dried after application and baked.
  • the coating compositions according to the invention are suitable for use in any type of industrial painting, for example for painting machines, vehicles, ships or structural components. They are of particular importance for vehicle painting. This may be either one-coat or multi-coat painting.
  • Coatings and finishes based on the coating compositions according to the invention are distinguished by improved weathering resistance, and especially by a very high light stability.
  • the invention relates to the use of light-stabilized microparticles according to the invention as constituents of coating compositions.
  • the dispersion which is obtained in the process according to the invention and which contains the polymer microparticles according to the invention there are also, in addition to the actual microparticles (characteristics: size distribution preferably 0.01-20 ⁇ m and crosslinking), proportions of other polymers which are not microparticles in the above sense. These do not interfere with the use in coating compositions, so that the dispersions obtained can as a rule be employed directly. If required, however, the microparticles can also be isolated as such or purified by removal of other polymer fractions. The latter can be accomplished, for example, by reprecipitation in suitable solvents, in which the uncrosslinked fractions are soluble.
  • microparticle dispersions from which the particles themselves can be isolated by suitable methods known per se, for example by spray-drying and especially by freeze-drying.
  • the isolated microparticles can then likewise be characterized by methods conventional in polymer chemistry, for example by means of light-scattering measurements, scanning electron microscopy, determination of the size distribution, of the form, and the like.
  • the microparticles have, in the ideal case, a spherical to oval shape.
  • the isolation and characterization of polymer microparticles have been described in many literature references, for example by Funke et al., Progr. Colloid Polymer Sci. 57, 48-53 (1975).
  • the apparatus used is a 1.5 liter sulfonation flask fitted with a stirrer, reflux condenser, thermometer and two rubber diaphragm inlets.
  • the flask is flame-heated in vacuo and filled with dry argon gas. Subsequently, the sulfonation flask is filled with the following components, always under argon:
  • TBAF 0.05 molar tetrabutylammonium fluoride trihydrate
  • reaction mixture is stirred under argon.
  • time schedule see below, the following components are then introduced into the reaction flask through the rubber diaphragm inlets by means of two different metering pumps:
  • microparticle granules which are filtered off with suction, washed with a little methanol and hexane, dried in a drying cabinet and then ground.
  • the light stabilizer content is 3%, relative to total solids.
  • the solution of the light-stabilized microparticles in 1,2-dimethoxyethane can also be used for the application as a coating.
  • the Mn/Mw values determined by GPC (gel permeation chromatography) are virtually the same.
  • the solids content is 43.5%.
  • Example 2 Taking 252 g of methyl methacrylate in place of the mixture I in Example 1 and taking 28.4 g of the piperidine light stabilizer 1-[2-methacryloyloxyethyl]-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine in place of the crosslinking agent II, and following the procedure of Example 1 in other respects, 243.8 g of a white microgel stabilized in the core are obtained.
  • the stabilizer content is 10.1%, relative to the total solids content.
  • Example 3 Using the mixture I described in Example 1 and the mixture, described in Example 3, of the crosslinking agent (mixture III), and following the procedure of Example 1 in other respects, a white microgel stabilized in the core and in the arms is again obtained.
  • the apparatus used is a 2.5 liter sulfonation flask fitted with a stirrer, reflux condenser, thermometer and rubber diaphragm inlet.
  • the flask is flame-heated in vacuo and filled with dry argon gas. Subsequently, the sulfonation flask is filled with the following components, always under argon:
  • TSAHF 2 tetrabutylammonium bifluoride
  • reaction mixture is stirred under argon.
  • time schedule see below, the following components are then introduced into the reaction flask through the rubber diaphragm by means of two different metering pumps:
  • reaction After a total reaction time of 100 minutes, the reaction is stopped by means of 20 g of methanol.
  • the resulting polymer microparticle dispersion has a solids content of 43.5%, containing about 2% of light stabilizer, relative to the total solids content.
  • TASHF 2 tris-(dimethylamino)-sulfonium bifluoride
  • Example 1 Using the same quantity of 2- 2-hydroxy-3-methyl-5-[2-(2-methacryloyloxy-cyclohexyloxycarbonyl)-ethyl]-phenyl -benzotriazole in place of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine in Example 1 and exactly following the procedure of Example 1 in other respects, a light-stabilized polymer microparticle dispersion with 3% of UV stabilizer, relative to the solids content, is likewise obtained, and this is used as such for applying a coating.
  • a polymer microparticle dispersion is obtained which is stabilized with 2.4% of light stabilizer, relative to the total solids content.
  • the stabilizer is incorporated in the "arms” and in the "core” of the microgels.
  • TSAHF 2 tetrabutylammonium bifluoride
  • the mixture is then stirred under argon and the following components are added successively in accordance with the precise time schedule given below.
  • the addition is made by means of two independent metering pumps.
  • the resulting polymer microparticle dispersion has a solids content of 41.2% and contains about 2% of light stabilizer, relative to the total solids content.
  • the reaction is strongly exothermic, so that it is cooled with ice/water to maintain an internal temperature of 65° C. After a reaction time of 100 minutes, the reaction in the slightly yellowish, viscous polymer microparticle solution is stopped by means of 20 ml of methanol. The microparticles can be precipitated from hexane or methanol. This gives about 71.4 g of polymer microparticles stabilized in the "core". The light stabilizer content is 3%, relative to the total solids content.
  • Example 17 Using a mixture consisting of 124 g of methyl methacrylate and 7.4 g of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine in place of component II in Example 17 and exactly following the detailed procedure of Example 17 in other respects, 110 g of white stabilized polymer microparticles are obtained which contain 3% of light stabilizer, relative to the total solids content, both in the "arms" and in the "core".
  • the apparatus used is a 2.5 liter sulfonation flask fitted with a stirrer, reflux condenser, thermometer and rubber diaphragm inlet.
  • the flask is flame-heated in vacuo and filled with dry argon gas.
  • the sulfonation flask is then charged with the following components, always under argon:
  • TSAHF 2 tetrabutylammonium bifluoride
  • reaction mixture is stirred under argon.
  • the following components are then added to the reaction flask through the rubber diaphragm by means of two different metering pumps in accordance with a precise time schedule (see below):
  • the resulting polymer microparticle dispersion has a solids content of 43.5%, containing about 2% of light stabilizer, relative to the total solids content.
  • Example 21 The same apparatus with the same preparations as in Example 21 is used again. Under argon,
  • TSAHF 2 tetrabutylammonium bifluoride
  • the resulting polymer microparticle dispersion has a solids content of 41.2% and contains about 2% of light stabilizer, relative to the total solids content.
  • the light-stabilized star microparticles obtained according to Examples 1-20 are processed in a curable coating composition.
  • microparticles are, as an about 30% solution in butyl acetate, incorporated into an acrylate/melamine clear coat in such a way that their content corresponds to 15% (relative to the solids content of the clear coat).
  • the coating composition obtained is diluted with a 13:6:1 mixture of xylene/butanol/butylglycol acetate up to sprayability, sprayed onto a prepared aluminium sheet (coil coat, filler, silver-metallic basecoat) and baked at 130° C. for 30 minutes. This gives a dry film thickness of about 45 ⁇ m of clear coat.
  • a coating mixture which contains unstabilized microparticles (prepared without addition of light stabilizer) in the same quantitative ratio, but in other respects is prepared and applied in the same way as above, is used as a comparison.
  • the specimens are tested both by accelerated weathering (®UVCON or ®Xenon weatherometer from Atlas Corporation) and by outside weathering in Florida.
  • the stabilized specimens each show better gloss retention and longer freedom from cracks than the unstabilized comparison specimen.
  • Example 27 The procedure followed is as in Example 27, but with the difference that the respective microparticles are not added to the finished coating mixture described in Example 27 but, instead, 15% (relative to solids content) of the acrylate component ®Uracron 2263 XB are replaced by the respective microparticles.
  • the coating mixture is processed and tested as in Example 27.
  • the stabilized specimens again show better gloss retention and longer freedom from cracks than the unstabilized comparison specimen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)
  • Dental Preparations (AREA)
US07/202,741 1987-06-04 1988-06-03 Light-stabilized star polymer microparticles Expired - Lifetime US4880859A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2114/87 1987-06-04
CH211487 1987-06-04

Publications (1)

Publication Number Publication Date
US4880859A true US4880859A (en) 1989-11-14

Family

ID=4226207

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/202,741 Expired - Lifetime US4880859A (en) 1987-06-04 1988-06-03 Light-stabilized star polymer microparticles

Country Status (12)

Country Link
US (1) US4880859A (de)
EP (1) EP0293871B1 (de)
JP (1) JP2739058B2 (de)
KR (1) KR960001218B1 (de)
AT (1) ATE87012T1 (de)
AU (1) AU609487B2 (de)
BR (1) BR8802719A (de)
CA (1) CA1304527C (de)
DE (1) DE3879275D1 (de)
ES (1) ES2060620T3 (de)
MX (1) MX168911B (de)
ZA (1) ZA883942B (de)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5041310A (en) * 1990-06-21 1991-08-20 Becton, Dickinson And Company Process for uniform coating of polymer particles with an additive
US5112912A (en) * 1989-03-21 1992-05-12 Ciba-Geigy Corp. Process for modifying acrylate copolymers
US5189084A (en) * 1989-12-21 1993-02-23 Ciba-Geigy Corporation Process for incorporating o-hydroxyphenyl-s-triazines in organic polymers
US5298033A (en) * 1989-03-14 1994-03-29 Ciba-Geigy Corporation Ultraviolet absorbing lenses and methods of manufacturing thereof
US5476882A (en) * 1985-12-06 1995-12-19 Ciba-Geigy Corporation Light-stabilized polymer microparticles
US5480927A (en) * 1994-05-20 1996-01-02 Ciba Geigy Corporation Method of increasing the concentration of radiation-absorbing agents in optical and ophthalmic lenses
US5518818A (en) * 1992-02-05 1996-05-21 Toray Industries, Inc. Primer and multilayer coated article
US6252032B1 (en) * 1999-07-07 2001-06-26 Minimed Inc. UV absorbing polymer
US6355718B1 (en) 1998-07-10 2002-03-12 E. I. Du Pont De Nemours And Company Microgels and process for their preparation
WO2003040218A1 (en) * 2001-11-09 2003-05-15 Polymerat Pty Ltd Porous polymer films
US6737528B2 (en) * 2001-02-22 2004-05-18 Council Of Scientific And Industrial Research Vinylic hindered amine light stabilizers
US20040236050A1 (en) * 2003-05-19 2004-11-25 Lundquist Eric G. High solids process for preparing polymeric nanoparticles
US20060094830A1 (en) * 2004-11-04 2006-05-04 Wayne Devonport High solids preparation of crosslinked polymer particles
US20150259280A1 (en) * 2012-10-23 2015-09-17 Basf Se Ethylenically Unsaturated Oligomers

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0296391B1 (de) * 1987-06-04 1993-07-07 Ciba-Geigy Ag Lichtstabilisierte, epoxygruppenhaltige Polymermikropartikel
DE69115535T2 (de) * 1990-03-23 1996-06-13 Ici Plc Polymere
GB9006557D0 (en) * 1990-03-23 1990-05-23 Ici Plc Polymers
AUPP337298A0 (en) * 1998-05-07 1998-05-28 University Of Melbourne, The Process for microgel preparation
KR100550224B1 (ko) * 1998-12-14 2006-02-08 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 입체장애 아민 화합물
JP4873782B2 (ja) * 1998-12-23 2012-02-08 チバ ホールディング インコーポレーテッド 低い多分散性を有するポリマー状安定剤
JP4496964B2 (ja) * 2005-01-14 2010-07-07 株式会社デンソー 車両用トンネル検出装置および車両用ライト制御装置

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272891A (en) * 1964-10-14 1966-09-13 American Cyanamid Co Stabilizing polymers with alkenoylamido- and phenylbenzatriazoles
US3318866A (en) * 1964-04-13 1967-05-09 Upjohn Co Process for making partial o-acylates of lincomycin
US3342850A (en) * 1963-01-04 1967-09-19 Eastman Kodak Co 2', 6-disubstituted phenyl salicylates
EP0003166A1 (de) * 1978-01-10 1979-07-25 Imperial Chemical Industries Plc Überzugszusammensetzungen
US4264678A (en) * 1979-05-29 1981-04-28 Gaf Corporation Core-shell polymers
US4414372A (en) * 1982-06-17 1983-11-08 E. I. Du Pont De Nemours & Co. Process for preparing living polymers
US4417034A (en) * 1981-06-30 1983-11-22 E. I. Du Pont De Nemours & Co. Living polymers and process for their preparation
US4419471A (en) * 1981-09-04 1983-12-06 Gaf Corporation Core-shell polymers
EP0119051A1 (de) * 1983-03-10 1984-09-19 BASF Corporation Verfahren zum Überziehen eines Substrats, Überzugszusammensetzung und überzogener Gegenstand
US4508880A (en) * 1981-06-30 1985-04-02 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
WO1986000626A1 (en) * 1984-07-05 1986-01-30 E.I. Du Pont De Nemours And Company Acrylic star polymers
US4618638A (en) * 1981-11-05 1986-10-21 Ciba-Geigy Corporation Compositions containing alpha-cyanocinnamate ultraviolet-absorbing stabilizers substituted by an aliphatic hydroxyl group
US4695607A (en) * 1984-07-05 1987-09-22 E. I. Du Pont De Nemours And Company Group transfer processes for acrylic star polymers

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3335625A1 (de) * 1983-09-30 1985-04-11 Siemens AG, 1000 Berlin und 8000 München Verfahren und vorrichtung zur speicherung der messdaten aus teilbereichen eines sputterkraters, der in einem sekundaerionen-massenspektrometer erzeugt und analysiert wird
JPS60108458A (ja) * 1983-11-18 1985-06-13 Nippon Erasutomaa Kk 熱可塑性エラストマ−組成物
JPS6142554A (ja) * 1984-08-04 1986-03-01 Asahi Chem Ind Co Ltd ブロツク共重合体の組成物
US4806605A (en) * 1987-01-27 1989-02-21 E. I. Du Pont De Nemours And Company Monomers and initiators for group transfer polymerization
JPS6351442A (ja) * 1988-02-01 1988-03-04 Japan Synthetic Rubber Co Ltd ブロツク共重合体組成物

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3342850A (en) * 1963-01-04 1967-09-19 Eastman Kodak Co 2', 6-disubstituted phenyl salicylates
US3318866A (en) * 1964-04-13 1967-05-09 Upjohn Co Process for making partial o-acylates of lincomycin
US3272891A (en) * 1964-10-14 1966-09-13 American Cyanamid Co Stabilizing polymers with alkenoylamido- and phenylbenzatriazoles
EP0003166A1 (de) * 1978-01-10 1979-07-25 Imperial Chemical Industries Plc Überzugszusammensetzungen
US4264678A (en) * 1979-05-29 1981-04-28 Gaf Corporation Core-shell polymers
US4417034A (en) * 1981-06-30 1983-11-22 E. I. Du Pont De Nemours & Co. Living polymers and process for their preparation
US4508880A (en) * 1981-06-30 1985-04-02 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4419471A (en) * 1981-09-04 1983-12-06 Gaf Corporation Core-shell polymers
US4618638A (en) * 1981-11-05 1986-10-21 Ciba-Geigy Corporation Compositions containing alpha-cyanocinnamate ultraviolet-absorbing stabilizers substituted by an aliphatic hydroxyl group
US4414372A (en) * 1982-06-17 1983-11-08 E. I. Du Pont De Nemours & Co. Process for preparing living polymers
US4524196A (en) * 1982-06-17 1985-06-18 E. I. Du Pont De Nemours And Company Process for preparing "living" polymers
EP0119051A1 (de) * 1983-03-10 1984-09-19 BASF Corporation Verfahren zum Überziehen eines Substrats, Überzugszusammensetzung und überzogener Gegenstand
WO1986000626A1 (en) * 1984-07-05 1986-01-30 E.I. Du Pont De Nemours And Company Acrylic star polymers
US4695607A (en) * 1984-07-05 1987-09-22 E. I. Du Pont De Nemours And Company Group transfer processes for acrylic star polymers

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Gomez, Polymer Preprints (Amer. Chem. Soc. Polym. Chem. Div.), vol. 28, No. 1 (1987), pp. 209 210. *
Gomez, Polymer Preprints (Amer. Chem. Soc. Polym. Chem. Div.), vol. 28, No. 1 (1987), pp. 209-210.
Stinson, C & EN (4/87), pp. 43 46. *
Stinson, C & EN (4/87), pp. 43-46.

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5476882A (en) * 1985-12-06 1995-12-19 Ciba-Geigy Corporation Light-stabilized polymer microparticles
US5298033A (en) * 1989-03-14 1994-03-29 Ciba-Geigy Corporation Ultraviolet absorbing lenses and methods of manufacturing thereof
US5399692A (en) * 1989-03-14 1995-03-21 Ciba-Geigy Corporation Ultraviolet absorbing benzophenone sulfonic acid derivatives
US5112912A (en) * 1989-03-21 1992-05-12 Ciba-Geigy Corp. Process for modifying acrylate copolymers
US5189084A (en) * 1989-12-21 1993-02-23 Ciba-Geigy Corporation Process for incorporating o-hydroxyphenyl-s-triazines in organic polymers
US5041310A (en) * 1990-06-21 1991-08-20 Becton, Dickinson And Company Process for uniform coating of polymer particles with an additive
US5518818A (en) * 1992-02-05 1996-05-21 Toray Industries, Inc. Primer and multilayer coated article
US5480927A (en) * 1994-05-20 1996-01-02 Ciba Geigy Corporation Method of increasing the concentration of radiation-absorbing agents in optical and ophthalmic lenses
US6355718B1 (en) 1998-07-10 2002-03-12 E. I. Du Pont De Nemours And Company Microgels and process for their preparation
US6646055B2 (en) 1998-07-10 2003-11-11 E. I. Du Pont De Nemours And Company Microgels and process for their preparation
US6252032B1 (en) * 1999-07-07 2001-06-26 Minimed Inc. UV absorbing polymer
US6737528B2 (en) * 2001-02-22 2004-05-18 Council Of Scientific And Industrial Research Vinylic hindered amine light stabilizers
WO2003040218A1 (en) * 2001-11-09 2003-05-15 Polymerat Pty Ltd Porous polymer films
US20040236050A1 (en) * 2003-05-19 2004-11-25 Lundquist Eric G. High solids process for preparing polymeric nanoparticles
US6858299B2 (en) 2003-05-19 2005-02-22 Rohm And Haas Company High solids process for preparing polymeric nanoparticles
US20060094830A1 (en) * 2004-11-04 2006-05-04 Wayne Devonport High solids preparation of crosslinked polymer particles
US7504466B2 (en) 2004-11-04 2009-03-17 Rohm And Haas Company High solids preparation of crosslinked polymer particles
US20150259280A1 (en) * 2012-10-23 2015-09-17 Basf Se Ethylenically Unsaturated Oligomers
CN105051012A (zh) * 2012-10-23 2015-11-11 巴斯夫欧洲公司 含有聚合物稳定剂基团的烯属不饱和低聚物
US9394244B2 (en) * 2012-10-23 2016-07-19 Basf Se Ethylenically unsaturated oligomers
CN105051012B (zh) * 2012-10-23 2019-01-04 巴斯夫欧洲公司 含有聚合物稳定剂基团的烯属不饱和低聚物

Also Published As

Publication number Publication date
AU609487B2 (en) 1991-05-02
MX168911B (es) 1993-06-14
AU1741888A (en) 1988-12-08
ES2060620T3 (es) 1994-12-01
KR890000529A (ko) 1989-03-15
EP0293871A2 (de) 1988-12-07
ZA883942B (en) 1989-02-22
EP0293871B1 (de) 1993-03-17
JP2739058B2 (ja) 1998-04-08
KR960001218B1 (ko) 1996-01-24
CA1304527C (en) 1992-06-30
JPS641712A (en) 1989-01-06
EP0293871A3 (de) 1991-01-09
ATE87012T1 (de) 1993-04-15
DE3879275D1 (de) 1993-04-22
BR8802719A (pt) 1988-12-27

Similar Documents

Publication Publication Date Title
US4880859A (en) Light-stabilized star polymer microparticles
US5476882A (en) Light-stabilized polymer microparticles
US4894399A (en) Light-stabilized polymer microparticles containing epoxy groups
US4511596A (en) Process for the electron beam curing of coating compositions
EP0434608B1 (de) Stabilisiertes organisches Material
EP0309401B2 (de) Stabilisierung einer Beschichtung mit sterisch gehinderten N-hydroxysubstituierten Aminen
JPH011712A (ja) 光安定化スターポリマーミクロ粒子
US5106891A (en) Light stabilized coating compositions containing a mixture of 2-hydroxyphenylbenzotriazole and 2-hydroxyphenyltriazine
CA1339741C (en) N-acyloxy hindered amine stabilizers
US5420204A (en) Light-stabilised copolymer compositions as paint binders
US5124378A (en) Stabilization of ambient cured coatings
US6187919B1 (en) Stabilized organic material
US4284485A (en) Photocurable compositions
JPH02389B2 (de)
JPH011764A (ja) エポキシ基を含有する光安定化ポリマーミクロ粒子、その製造方法、それらを含有する分散系及び分散系を含有する被覆組成物
JP2552464B2 (ja) ポリマ−ミクロ及び該粒子の製造方法
US5204422A (en) Peroxide free radical initiators containing hindered amine moieties with low basicity
US5140081A (en) Peroxide free radical initiators containing hindered amine moieties with low basicity
US5302497A (en) Photosensitive organic polymeric material containing UV absorbers
JPH1180485A (ja) アクリルエマルジョン組成物
US5051511A (en) Peroxide free radical initiators containing hindered amine moieties with low basicity
CZ287258B6 (cs) Stabilizovaný organický polymer
HK1004562B (en) Stabilized organic material

Legal Events

Date Code Title Description
AS Assignment

Owner name: CIBA-GEIGY CORPORATION, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CIBA-GEIGY AG, A SWISS CO.;REEL/FRAME:005216/0106

Effective date: 19890804

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

AS Assignment

Owner name: CIBA SPECIALTY CHEMICAL CORPORATION, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CIBA-GEIGY CORPORATION;REEL/FRAME:008401/0522

Effective date: 19961227

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12